EP0588973A1 - Process for the preparation of a phenol - Google Patents
Process for the preparation of a phenolInfo
- Publication number
- EP0588973A1 EP0588973A1 EP92914859A EP92914859A EP0588973A1 EP 0588973 A1 EP0588973 A1 EP 0588973A1 EP 92914859 A EP92914859 A EP 92914859A EP 92914859 A EP92914859 A EP 92914859A EP 0588973 A1 EP0588973 A1 EP 0588973A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- process according
- phenol
- carried out
- formation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 230000007717 exclusion Effects 0.000 claims description 3
- 238000005895 oxidative decarboxylation reaction Methods 0.000 claims description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims 1
- 230000007812 deficiency Effects 0.000 claims 1
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001559 benzoic acids Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WLLASMDMMUPSMP-UHFFFAOYSA-N benzoic acid;copper Chemical compound [Cu].OC(=O)C1=CC=CC=C1 WLLASMDMMUPSMP-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- -1 cylcoalkyl Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the invention relates to a process for the preparation of a phenol by an oxidative decarboxylation in the gas phase of a corresponding arylcarboxylic acid in the presence of a Cu-containing catalyst.
- GB-A-762738 which is an equiavlent of NL-B-90.684 already discloses such a process, wherein the oxidation, the decarboxylation as well as the hydrolysis are effected in a single process step, at a temperature of at least 200°C, preferably 230-250°C.
- the process according to the invention provides a process for the preparation of a phenol from the corresponding arylcarboxylic acid in the gas phase, with virtually complete prevention of tar formation.
- a process is obtained which combines high preparation selectivities with an economically attractive embodiment.
- the process according to the invention is characterized in that the following process steps are carried out: a) Supplying an oxidant-containing gas mixture to the catalyst bed under such conditions that tar formation virtually absent, b) Supplying arylcarboxylic acid and steam with exclusion of oxygen, resulting in formation of gaseous phenol.
- arylcarboxylic acid is understood to be a compound having the following structure:
- R 1 through R 5 may be hydrogen (on the proviso that at least R 1 or R 5 is hydrogen) or organic groups, which have a so-called Hammett constant of between -1 and +2.
- a description of this Hammett or ⁇ value, which represents a measure of the influence of the group on the reactivity of the arylcarboxylic acid, can be found in J. March, Advanced Organic Chemistry 1989, pages 242-250; see in particular table 4 on page 244.
- the groups that can be used therefore are: C j ⁇ -Cg alkyl, cylcoalkyl, aryl, arylalkyl, amino, halogen, nitro.
- Esters and anhydrides of (I) are also suitable, while the groups may also be connected with each other via ring system, as is the case for instance in naphthalene carboxylic acid (substituted or not).
- Multiple arylcarboxylic acids, such as trimellitic acid and pyromellitic acid, can also be used as starting material. Mixtures of the arylcarboxylic acids described above can also be used in the process according to the invention.
- the oxidation of the Cu-containing catalyst involving conversion of copper into Cu(II), is a first reaction step in the process. It brings about an increase in the degree of oxidation of the copper.
- the oxidation of the copper-containing catalyst proceeds well particularly when carried out using an oxygen-containing gas. Air, whether or not enriched with oxygen or oxygen-depleted, can very well be used for this. Other oxidizing gases can also be used, e.g. N 2 0- or
- no tar is formed.
- This can be achieved by various measures. For instance it can be ensured that no phenol is absorbed to the catalyst any more, hence that the catalyst is essentially free of phenol. This can be accomplished by stripping with steam or an inert gas at the end of the second step. Or for instance the temperature of the catalyst bed in this step can be kept below 200°C, preferably between 150-190°C (because the rate of oxidation of Cu is high and tar formation does not occur until the temperature exceeds 200°C, in the presence of phenol). It is also possible to apply a higher temperature (e.g. 191-270°C) and keep the contact time between the reaction mixture and the oxygen short (e.g. 0.1-5 minutes), so that not all the copper is converted into the Cu(II) form.
- the catalyst can be applied onto a carrier, consisting for instance of oxides of silicon, titanium or cadmium, of for instance of carbon.
- the catalyst is used immobilized on a carrier.
- Silica is preferably used as carrier.
- the catalyst load will as a rule be 5-40 wt.% metal on carrier.
- a high degree of loading contributes to a high conversion per volume unit.
- This co-catalyst can be chosen in particular from groups III through VIII as well as from the group of the lanthanides and actinides of the Periodic System of the Elements. These components have an effect on the oxidative capacity of the Cu in the catalyst.
- the catalyst used may for instance consist of copper, zirconium and, if desired, an alkali metal or an alkali earth metal such as sodium, potassium, lithium or magnesium. Also, rare earths (atom numbers 37 through 71) or zirconium, silver, vanadium, chromium, molybdenum, hafnium and tungsten or mixtures thereof in combination with copper can be used.
- the second step in the process according to the invention comprises a combination of a reduction and the formation of phenol, in which process carbondioxide (C0 2 ) is released.
- the pressure under which the second process step is performed is not critical, but the advantage of raising the pressure to above atmospheric level is that it has a favourable effect on the reaction kinetics.
- the pressure to be applied will generally be between 0.1 and 2.5 MPa; higher pressures, though allowable, do not yield substantial improvements of the process.
- reaction products are subjected to an upgrading operation in order to separate and recover the phenol obtained. This can be done in ways known by themselves, for instance by distillation.
- the bottom flow of the distillation which may contain non-converted arylcarboxylic acid, can be recycled to the process, optionally after a purification step.
- the catalyst can be applied in the form of a fixed or moving beds.
- the two-step reaction can be carried out intermittently, successively supplying for a short time an oxygen-containing gas to e.g. a fixed-bed reactor and then - with exclusion of oxygen - having the second step take place.
- the oxidative gas mixture can be supplied again.
- the two-step process can also be carried out continuously by having the oxidation step take place in the first reactor of a multiple reactor system and then bringing the catalyst, preferably in a moving bed, to a second reactor, where the second step takes place. In that case the reactors can be fully adapted to the desired requirements.
- the process according to the invention is suitable in particular for the preparation of unsubstituted phenol from unsubstituted benzoic acid.
- This phenol can be used for instance as starting material both for phenol-formaldehyde resins and for the preparation of caprolactam, starting material for nylon-6, or for the preparation of bisphenol-A. 5
- the invention will now be elucidated in the following examples, which should not be construed as limiting the invention.
- Tests were performed using a set-up as represented in the annexed diagram, in which A represents a steam-generating device (H 2 0/N 2 mixture), B a benzoic acid evaporator and C an air supply device. The three flows go to the reactor bed in D. E, F and G are coolers, cooling the
- H is the analysis section for the offgas mixture.
- the reactor consisted of a packed bed of about 2.5 ml, filled with copperoxide on silica.
- the gas flows from A, B and C were adjustable, products in E through H were analyzed using gas
- the catalyst was oxidized with air for 30 seconds.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9100582A BE1004950A4 (nl) | 1991-06-14 | 1991-06-14 | Werkwijze voor de bereiding van een fenol. |
| BE9100582 | 1991-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0588973A1 true EP0588973A1 (en) | 1994-03-30 |
Family
ID=3885569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92914859A Withdrawn EP0588973A1 (en) | 1991-06-14 | 1992-06-10 | Process for the preparation of a phenol |
Country Status (12)
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8201664A (nl) * | 1982-04-22 | 1983-11-16 | Stamicarbon | Werkwijze voor de bereiding van gesubstitueerd of ongesubstitueerd fenol en katalysatoren daarvoor. |
-
1991
- 1991-06-14 BE BE9100582A patent/BE1004950A4/nl not_active IP Right Cessation
-
1992
- 1992-06-03 TW TW081104391A patent/TW224087B/zh active
- 1992-06-10 WO PCT/NL1992/000101 patent/WO1992022519A1/en not_active Application Discontinuation
- 1992-06-10 JP JP5500809A patent/JPH06508616A/ja active Pending
- 1992-06-10 AU AU22752/92A patent/AU2275292A/en not_active Abandoned
- 1992-06-10 BR BR9206152A patent/BR9206152A/pt not_active Application Discontinuation
- 1992-06-10 SK SK1407-93A patent/SK140793A3/sk unknown
- 1992-06-10 FI FI935588A patent/FI935588L/fi unknown
- 1992-06-10 CZ CS932690A patent/CZ269093A3/cs unknown
- 1992-06-10 EP EP92914859A patent/EP0588973A1/en not_active Withdrawn
-
1993
- 1993-12-14 BG BG98301A patent/BG98301A/xx unknown
-
1994
- 1994-11-11 EE EE9400222A patent/EE9400222A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9222519A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EE9400222A (et) | 1996-02-15 |
| AU2275292A (en) | 1993-01-12 |
| BR9206152A (pt) | 1994-12-06 |
| CZ269093A3 (en) | 1994-04-13 |
| JPH06508616A (ja) | 1994-09-29 |
| SK140793A3 (en) | 1994-08-10 |
| FI935588A0 (fi) | 1993-12-13 |
| BG98301A (bg) | 1995-01-03 |
| WO1992022519A1 (en) | 1992-12-23 |
| FI935588A7 (fi) | 1993-12-13 |
| BE1004950A4 (nl) | 1993-03-02 |
| FI935588L (fi) | 1993-12-13 |
| TW224087B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1994-05-21 |
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